Psychological inflexibility is a transdiagnostic dimension associated to psychological distress and poor mental health and quality of life. While multiple instruments have been developed for the assessment of patterns of inflexible responding to aversive private events (e.g., unwanted cognitions and emotions), the Experiential Approach Scale (EAS) is the first instrument specifically designed to assess inflexible responding to appetitive private events (e.g., desired affective states). In this study, we explored the factor structure, internal consistency, and convergent validity of a Spanish adaptation of the EAS with a convenience sample of college students from Spain (n = 206; 79% female). A two-factor solution demonstrated very good fit to the data and was similar to the original two-subscale EAS structure: Anxious Clinging and Experience Prolonging. The scale showed adequate overall (α = 0.85) and subscale (αs: 0.90 and 0.89) internal consistency. Unlike the original instrument, both subscales were uncorrelated. Anxious Clinging correlated positively with experiential avoidance and with measures of negative affect and psychopathology, and negatively with positive affect, subjective happiness, and life satisfaction. In turn, Experience Prolonging correlated negatively with psychopathology and positively with positive affect, subjective happiness, and life satisfaction. Our results point to Anxious Clinging as the only EAS subscale contributing to psychological inflexibility.